WO2002005949A1

WO2002005949A1 - Absorbents and process for producing the same, absorbable constructs and absorbable articles

Info

Publication number: WO2002005949A1
Application number: PCT/JP2001/006111
Authority: WO
Inventors: Yoshihisa Ota; Yoshiyuki Iwasaki
Original assignee: Sanyo Chemical Industries, Ltd.
Priority date: 2000-07-18
Filing date: 2001-07-13
Publication date: 2002-01-24
Also published as: EP1325777B1; BR0113001B1; JP4141829B2; AU2001271051A1; WO2002005949A9; TWI306411B; DE60143706D1; EP1325777A4; CN1443092A; EP1325777A1; US7087669B2; JPWO2002005949A1; BR0113001A; US20040024104A1

Abstract

Absorbents comprising an water-absorbable resin and water-insoluble nonporous spherical monoparticles having an average diameter of 1 to 50 nm; a process for producing these absorbent by mixing the spherical monoparticles, which have been solubilized in water, with dry powdery particles of the water-absorbable resin; absorbable constructs composed of the above absorbent with a matrix wherein the amount of the absorbent ranges from 30 to 95% by weight based on the absorbable construct; and absorbable articles provided with the absorbable construct, a liquid-permeable sheet and an air-permeable back sheet. These absorbents, absorbable constructs and absorbable articles are excellent in the diffusion/absorption speed and absorption amount of a liquid within the resin even in case of absorbing a liquid containing water-insoluble or hardly water-soluble matters such as menstrual blood or feces.

Description

Description Microparticle-labeled protein and immunochromatography apparatus using the same Technical field The present invention relates to ί rescue particle-labeled protein used for immunological detection such as immunoagglutination and immunochromatography, and the use of the protein. Related to immunochromatography equipment. BACKGROUND ART Conventionally, labeling substances for protein labeling used for immunological detection include red gold colloid particles and blue colored latex particles. Labeled proteins produced using them are mainly used in the latex agglutination method and immunochromatography. However, blue latex has poor visibility to the naked eye, and blue latex is not suitable for use in blood assays where the red color is the background. Immunochromatography is a measurement method that uses a substance (eg, antibody) that specifically reacts with the substance to be measured as a material for detection means, utilizing the high specificity and detection sensitivity of the antigen-antibody reaction. This method is now widely used as a basic technology for in vitro diagnostics. Above all, a pregnancy diagnostic agent is a typical immunochromatography apparatus, and a typical structure thereof is disclosed in, for example, US Pat. No. 5,602,040. In this immunochromatography apparatus, a complex of hCG to be measured and a gold colloid-labeled antibody is formed using a colloidal gold-labeled antibody as a labeled protein and urine as a measurement sample, and the red color derived from the complex is formed. The presence or absence of a colored image is visually determined. Description Absorbent and method for producing same, absorbent structure, absorbent article

The present invention relates to an absorbent, a method for producing the same, an absorbent structure, and an absorbent article. More specifically, even if the liquid to be absorbed contains a water-insoluble component or a poorly water-soluble component such as menstrual blood, stool, etc., the absorbent has excellent diffusion absorption rate and absorption amount of the liquid to be absorbed into the absorbent resin, and an absorbent. The present invention relates to a manufacturing method, an absorbent structure, and an absorbent article. Background art

Conventionally, various methods have been proposed to improve the absorption rate of water-absorbent resin used as an absorbent for disposable diapers and the like.The concept is to increase the surface area of the water-absorbent resin to increase the contact area with the liquid to be absorbed. There are the following methods based on this.

a. A method in which a volatile solvent having a low boiling point is added to a stock polymerization solution in the process of producing a water-absorbent resin, and the volatile solvent is vaporized by the heat of polymerization to make the resin porous (Japanese Patent Laid-Open No. 59-18). No. 7 1 2);

b. A method of mixing a water-absorbing resin containing a carboxyl group and a polyolefin resin containing a glycidyl group with a cross-linking agent and a pyrolytic foaming agent, followed by heating and foaming to form a foam (Japanese Patent Application Laid-Open No. 63-2514). No. 37);

c. A method of obtaining a porous water-absorbent resin by dispersing and polymerizing a blowing agent comprising an azo compound containing an amino group in an aqueous solution containing an unsaturated monomer and a crosslinking agent (Republished Patent WO 96- 1 7 8 8 4 gazette);

d. A method of granulating fine particles using water or a hot-melt resin binder; e. A mixture of water-absorbent resin particles and porous inorganic particles, the weight ratio of which is from 109 to 900 The surface of the water-absorbent resin is within the range of the inorganic particles. Two

(JP-A-8-10616).

However, these methods have not been satisfactory in terms of performance and manufacturing method.

Recently, it has been proposed to incorporate a microscopic filler into a water-absorbent resin to improve the absorption rate by a method of increasing the surface area by 10% or more (International Publication WO 99Z03577).

However, although the absorption rate of the liquid to be absorbed containing water-insoluble components such as menstrual blood and stool and poorly water-soluble components is improved by this method, the demands on the market are further increased. Improvement of the absorption amount is desired.

The present inventors have conducted intensive studies in view of the above problems, and as a result, by using water-insoluble non-porous spherical single particles having a specific average particle size in combination with the water-absorbing resin, the diffusion and absorption of the liquid to be absorbed has been achieved. The inventors have found that the speed and the amount of absorption are improved, and arrived at the present invention. The present invention relates to an absorbent containing water-insoluble and poorly water-soluble components such as menstrual blood and stool, and has an excellent absorption and diffusion rate and absorption amount of the liquid to be absorbed into the absorbent resin. It is intended to provide a manufacturing method. Another object of the present invention is to provide an absorbent structure and an absorbent article which exhibit excellent absorption performance when the absorbent of the present invention is applied to sanitary articles such as sanitary napkins. Summary of the Invention

That is, the present invention is the following inventions (I) to (IV).

(I) An absorbent (C) comprising a water-absorbent resin (A) and water-insoluble non-porous spherical single particles (B) having an average particle diameter of 1 to 50 nm.

(I) A method for producing an absorbent (C), wherein the water-solubilized product of (B) is mixed with the dry powder particles of (A).

(Ii) an absorbent structure (F) comprising a matrix of the absorbent (C) and the fibrous material (E), wherein the amount of the absorbent (C) is F) 30 to 95% by weight of an absorbent structure (F).

(IV) An absorbent article (G) comprising the absorbent structure (F), a liquid-permeable sheet, and a breathable back sheet. Detailed Disclosure of the Invention

(Absorbent and its manufacturing method)

In the present invention, examples of the water-absorbent resin (A) include a crosslinked product of a starch-acrylic acid copolymer, a saponified product of a starch-acrylonitrile copolymer, a crosslinked product of a polyacrylate, and a self-crosslinked polyacrylate. , (Meth) acrylic ester crosslinked vinyl monoacetate copolymer, saponified product, isoptilenno maleic anhydride copolymer crosslinked product, polysulfonate crosslinked product, polyacrylate nopolysulfonate copolymer crosslinked product And cross-linked polyacrylic acid / polyacrylamide copolymers, cross-linked polyacrylamide and hydrolysates thereof, cross-linked polyvinyl pyrrolidone, cross-linked cellulose derivatives and the like.

Of these, preferred are polymerizable monomers containing carboxylate and Z or porphyric acid, which can absorb and hold a large amount of liquid by ionic osmotic pressure and have little water separation even when a load or external force is applied. Is a water-absorbent resin having as a main component, more preferably a crosslinked product of a starch-acrylate copolymer and a crosslinked polyacrylate.

When (A) is a resin in the form of a salt (neutralized salt), the type of salt and the degree of neutralization are not particularly limited. Examples of the type of salt include, for example, usually an alkali metal salt, preferably a sodium salt and a potassium salt, and the degree of neutralization with respect to acid groups is usually 50 to 90 mol%, preferably 60 to 80 mol%. It is. The neutralization may be performed before or after the polymerization.

The water-absorbent resin (A) of the crosslinked polyacrylate is a water-absorbent resin obtained by polymerizing a water-soluble monomer (a-1) and a first crosslinking agent (a-2). Four

Examples of the water-soluble monomer (a_l) used in the production of (A) include a radical-polymerizable water-soluble monomer having a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and salts thereof. Can be

Examples of the radically polymerizable water-soluble monomer having a hydroxyl group include unsaturated mono- or polycarboxylic acids [(meth) acrylic acid (meaning acrylic acid and Z or methacrylic acid. The same description is used hereinafter). Crotonic acid, sorbic acid, maleic acid, itaconic acid, cinnamic acid], salts thereof, and anhydrides thereof (eg, anhydrous maleic acid).

Examples of the radically polymerizable water-soluble monomer having a sulfonic acid group include, for example, fatty acid or aromatic vinyl sulfonic acid (vinyl sulfonic acid, aryl sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, etc.), (meth) acrylic alkyl Sulfonic acid [sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate], (meth) acrylamidoalkylsulfonic acid [2-acrylamide 2-methylpropanesulfonic acid, etc.] and salts thereof. Radical polymerizable water-soluble monomers having a phosphate group include, for example, (meth) acrylic acid hydroxyalkyl phosphate monoester [2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acrylic acid Roylloxyshyl phosphate and the like].

These may be used alone or in combination of two or more. Among these, preferred water-soluble monomers are radically polymerizable water-soluble monomers having a hydroxyl group and salts thereof, more preferably unsaturated mono- or polycarboxylic acids and salts thereof, and particularly preferably (meth) ) Acrylic acid and its salts.

The cross-linking agent used in the production of (A) includes a first cross-linking agent (a-2) used in combination with the polymerization of the above monomer, and, if necessary, drying and pulverization after polymerization to form particles. Surface crosslinking agent (second crosslinking agent; a-3). Examples of (a-12) include a crosslinking agent having two or more ethylenically unsaturated groups, A crosslinking agent having at least one functional group capable of reacting with a functional group of the body and having at least one ethylenically unsaturated group; and at least two functional groups capable of reacting with a functional group of a monomer And a cross-linking agent.

(i) Examples of the crosslinking agent having two or more ethylenically unsaturated groups include N, N'-methylenebis (meth) acrylamide, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol. Cole di (meth) acrylate, glycerin (di or tri) acrylate, trimethylolpropane triacrylate, triallylamine, triallyl cyanurate, triaryl isocyanurate, tetraaryloxetane, erythritol triaryl ether And the like.

(ii) As a cross-linking agent having at least one functional group capable of reacting with a functional group (for example, carbonyl group) of a monomer and having at least one ethylenically unsaturated group, a carboxylic acid ( Salt) a crosslinking agent having at least one functional group capable of reacting with a group, a hydroxyl group, an amino group, etc. and having at least one ethylenically unsaturated group, such as glycidyl (meth) acrylate And ethylenically unsaturated groups having a hydroxyl group such as N-methylol (meth) acrylamide and hydroxyethyl (meth) acrylate.

(iii) The crosslinking agent having at least two functional groups capable of reacting with the functional group of the monomer includes at least a functional group capable of reacting with a carboxylic acid (salt) group, a hydroxyl group, an amino group, or the like. A polyglycidyl ether compound having 2 to 10 epoxy groups in one molecule [ethylene glycol diglycidyl ether, glycerin-1,3-diglycidyl ether, glycerin triglycidyl ether] Polyethylene glycol (degree of polymerization 2 to 100) diglycidyl ether, polyglycerol (degree of polymerization 2 to 100) polyglycidyl ether, etc.]; divalent to 20-valent polyol compound [glycerin, 6

Ethylene glycol, polyethylene glycol (degree of polymerization: 2 to 100), etc .; divalent to 20-valent polyamine compounds (ethylene diamine, diethylene triamine, etc.); polyamine resins having a molecular weight of 200 to 500,000 (polyamide polyamine epichlorohydrin resin) , Polyamine epichlorohydrin resin, etc.), alkylene carbonate [eg, ethylene glycol], aziridine compound, and polyimine compound. These crosslinking agents may be used alone or in combination of two or more.

The amount of the first crosslinking agent (a-2) used is preferably 0.001 to 5.0% by mass based on the total mass of the monomer (a-1) and the first crosslinking agent (a-2). More preferably, it is 0.002 to 2.0% by mass, particularly preferably 0.003 to 1.6% by mass. When the amount of (a_ 2) is 0.001% by mass or more, the water retention Z blood retention / absorption ability becomes good, and when the amount is 5.0% by mass or less, the crosslinking is not too strong, and the water retention Z blood retention / Z absorption ability also increases. Does not drop.

The method for producing the water-absorbent resin (A) in the present invention may be a conventionally known method, for example, a solution polymerization method using an initiator, an emulsion polymerization method, a suspension polymerization method, a reverse phase suspension polymerization method, Examples include a thin film polymerization method and a spray polymerization method. Examples of the polymerization control method include an adiabatic polymerization method, a temperature-controlled polymerization method, and an isothermal polymerization method. When the suspension polymerization method or reverse phase suspension polymerization method is used as the production method, if necessary, a conventionally known dispersant, protective colloid, surfactant, or a mixture of one or more of these may be used. The polymerization is carried out in the presence. In the case of the reverse phase suspension polymerization method, polymerization is carried out using a conventionally known solvent such as cyclohexane, normal hexane, normal heptane and xylene. Preferred is a solution polymerization method using a polymerization initiator, and particularly preferred is an aqueous solution polymerization method because it does not require the use of an organic solvent or the like and is advantageous in production cost.

The initiator is not particularly limited as long as it is an azo-based initiator, a peroxide-based initiator, a redox-based initiator, or an organic halogen compound initiator. Can be used. Specifically, the following are mentioned.

(i) As the azo initiator, azobisisobutyronitrile, azobiscyanovaleric acid and a salt thereof, 2,2, -azobisamidinopropane dihydride chloride at the mouth of the mouth, 2,2'-azobis (2 —Amidinopropane) hydride chloride, 2,2'-azobis [2-methyl-N— (2-hydroxyethyl)] propionamide, etc .;

(ii) Peroxide initiators include inorganic peroxides [hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.], and organic peroxides [benzoyl peroxide, di-t —Butyl peroxide, cumene hydroperoxide, succinic peroxide, di (2-ethoxyshethyl) peroxide, etc .;

(iii) Redox initiators include reducing agents such as alkali metal sulfites or bisulfites, ammonium sulfite, ammonium bisulfite, ferric chloride, ferric sulfate, and ascorbic acid; and alkali metal persulfate. Salts, ammonium persulfate, hydrogen peroxide, organic peroxides and the like in combination with oxidizing agents are listed.

(iv) Examples of the halogen of the organohalogen compound initiator include fluorine, chlorine, bromine and iodine.

The organic halogen compound is not particularly limited, but is preferably selected from the group consisting of alkyl halides, octogenated alkyl phenyl ketones, halogenated alkyl carboxylic acids, and halogenated alkyl carboxylic acid alkyl esters from the viewpoint of polymerizability. It is an organic halogen compound having a halogen number of 1 to 10 or more and a carbon number of 1 to 15 or more. More preferably, tetrachloromethane, trichlorobromomethane, trichloroiodomethane, dichloromethylphenylketone, 1-bromo-1-methylethylcarboxylic acid, 1-bromo-1-methylethylcarboxy having 1 to 8 carbon atoms of the alkyl group Acid alkyl esters 8

(For example, methyl 1-promo-1-methylethylcarbonate, ethyl 1-bromo-1-methylethylcarbonate, octyl 1-bromo-1-methylethylcarboxylate, 1-bromo-1-methylethylcarboxylate Lauryl acid). Particularly preferred are dichloromethylphenyl ketone and alkyl 1-bromo-1-methylethylcarboxylates having 1 to 8 alkyl groups. These initiators may be used alone or in combination of two or more. Preferred are azo initiators, redox initiators and combinations thereof.

The amount of the initiator to be used is preferably from 0.05 to 0.5% by mass, more preferably from 0.007 to 0.4% by mass, based on the total mass of (a-1) and (a-2). And particularly preferably from 0.009 to 0.3% by mass.

Further, in order to improve the absorption performance of the water-absorbent resin (A) of the present invention, it is preferable to increase the molecular weight of (A), and for this purpose, for example, (A) is one of the following ① to ③ Can be obtained in a way.

(1) Polymerize when the concentration of the total amount of (a-1) and (a-2) in the polymerization solution is 20% by mass or less.

(2) 70% by mass or more of the polymerizable monomers ((a-1) and (a-2)) in the polymerization solution at a polymerization temperature of 6 or less and preferably ± 5 ° C, more preferably 2 ° C The polymerization is carried out at a constant temperature within the temperature control range.

③ Polymerization is carried out in the presence of a complex compound (d) of a metal element (dl) and a ligand (d2) of an anion or neutral molecule.

As the water-absorbing resin (A) of the present invention, those described in (3) are particularly preferable. The complex compound (d) is a complex compound of a metal element (dl) and a ligand of an anion or a neutral molecule (d 2), and (d 1) is a complex compound of an anion or a neutral molecule. It has a structure surrounded by a ligand (d2).

(dl) is not particularly limited as long as it is a metal element. For example, a main group element metal, a group IA element metal (lithium, sodium, potassium, cesium, etc.), 9

Group IB element metals (copper, silver, gold, etc.), Group IIA element metals (magnesium, calcium, norium, etc.), Group III element metals (scandium, yttrium), Group III element metals (aluminum, gallium, indium, thallium) Group IVA element metals (titanium, zirconium, hafnium), group IVB element metals (tin, zinc, etc.), group VA element metals (vanadium, niobium, tantalum), group VB element metals (antimony, bismuth, etc.) , Group VIA elemental metals (chromium, molybdenum, tungsten), Group VIB elemental metals (tellurium, polonium, etc.), Group VIIA elemental metals (manganese, technetium, rhenium), Group VIII element metals (iron, cobalt, nickel, Ruthenium, rhodium, palladium, osmium, iridium, platinum), lanthanide-noid metal ( Lanthanum, cerium, etc.), Akuchinoido group elements metals (actinium, thorium, etc.) and the like. From the viewpoint of the polymerizability of the vinyl polymerizable monomer, preferred are group IB, group 、, group IVA, group VA, group VIA, group VIA, group VIII, and lanthanoid group metal, and more preferably group IB, Group VIII and lanthanoid group element metals, particularly preferably Group IB and Group VIII element metals having 4 to 6 cycles. Most preferably, it is a group VIII element metal (ruthenium, rhodium, palladium) having five periods, from the viewpoint of workability and ease of handling.

The (d l) is usually present as a cation, but may be other than a cation, for example, neutral such as iron pentacarbonyl.

(d 2) is not particularly limited as long as it is an anion or a ligand that is a neutral molecule. For example, an anion of an atom selected from hydrogen, halogen, and nitrogen, oxygen, phosphorus, and sulfur Compounds having one or more kinds of atoms selected from the group consisting of: ③ One or more kinds selected from conjugated compounds.

Specifically, the following are mentioned.

① Anion of atom selected from hydrogen and halogen;

Anions of hydrogen, fluorine, chlorine, bromine and iodine; Ten

② Compounds having one or more atoms selected from the group consisting of nitrogen, oxygen, phosphorus, and sulfur include the following. Preferably, it is a compound having a molecular weight of 1,000 or less (a compound having a possibility of coordination of two or more kinds is classified into one of the coordinable groups).

(1) Tertiary phosphine compounds having 1 to 4 or more phosphorus atoms and 3 to 42 or more carbon atoms;

Trimethylphosphine, triethylphosphine, getylphenylphosphine, triphenylphosphine (hereinafter PPh ₃ ), ortho-phenylenebis (diphenylphosphine), orthophenylenebis (dimethylphosphine), orthophenylenebis ( Dimethylphosphine), ortho-phenylenebis (ethylphenylphosphine), 1,2-bis (diphenylphosphino) ethane, 1,2-bis (dimethylphosphino) ethane (dppe), 1, 2 -Bis (getylphosphino) ethane, 1,2-bis (ethylphenylphosphino) ethane, 1,2-bis (diphenylphosphino) methane (dp pm), 1,2-bis (dimethyl) Phosphino) methane, 1,2-bis (getylphosphino) methane, 1,2-bis (ethylphenylphosphino) methane Tris (di-phenylpropyl phosphino ethyl) phosphine, tris (GETS chill phosphino ethyl Le) phosphine, Bok squirrel (dimethyl Le phosphino ethyl) phosphine, tri scan (E chill phenylalanine phosphino ethyl) phosphine;

(2) ammonia or amines having 1 to 4 or more nitrogen atoms and 0 to 44 or more carbon atoms;

(2-1) Nitrogen number 1; pyridine (hereinafter abbreviated as py), getylamine, salicylamine, aminoethaneselenol, 2-hydroxy-6-methylpyridin, 2-getylaminoenol, bis (2-aminoethyl) amide, 2-aminoamine, 2-aminoethanol, β-alanine, 2-hydroxy-16-methylpyridine, 3-salicylideneamino_1-propanol, 2-pi 11

Oral lidone, 8-quinolinol, salicylaldimine, hypicolin etc .;

(2-2) Nitrogen number 2; ethylenediamine (hereinafter en), proprendiamine, trimethylenediamine, 1,2-cyclohexanediamine, N, N-ethylethylenediamine, N, N-dimethyl Ethylenediamine, salicylideneethylenediamine, N-ethylsalicylicaldiamine, bis (benzoylacetone) ethylenediamine 1,2-diamine 1,1'-dimethylethane, 2,2'-bipyridine (hereinafter bpy), 2,2,2 1-biviridine (hereinafter b py), 2,2, -bipyridine-1-yne, 2,2'-bipyridine-N, N, dioxide, dicyandiamidine, (aminoiminomethyl) urea, [(2-aminoethyl) Amino)] — 1—propanol, 2 — [(3-aminopropyl) amino] ethanol, N—2 [2- (Jetylamino) ethyl] 1-3-amino-1-propanol, [2— (Methylamino) ethyl] amine, imidazole, N, N'-disatilidenetrimethylenediamine, 4,6,6, -trimethyl- 3,7-diazanona-3_-1, 9-diol, N, N, Ν ', N'-tetramethylethylenediamine, 1,8-naphthyridine and the like;

(2-3) Nitrogen number 3 or more; methylenetriamine, triethylenetetramine, tetraethylpentamine, N, N'-bis (2-aminobenzylidene) ethylenediamine, tris 12- (methylamino) ethyl] amine Aminopyridin, 1,3-bis [bis (2-pyridylethyl) aminomethyl] benzene, 4-dimethylamino_2,3-dimethyl-11-phenyl-1-5-pyrazolane, biguanide, imidodicarbonimidodiamide, biuret, Powerbamoyl guanidine, phthalocyanine, Ν, Ν, N ', N'-tetrakis (2-aminodiethyl) ethylenediamine, 1,2,3-triaminopropane, tris (2-benzimidazolylmethyl) amine, tetrakis (2-) Pyridylmethyl) ethylenediamine, 2,2 ', 2 "monoterpyridine, 1,4,7,10-tetraazadecane, 1, 4, 8, 11—tetraazadecane, 1, 5, 8, 12

1 2—Tetraazadodecane, 1, 4, 8, 1 1—

Can, ethylenebis (biguanide), tetraphenylporphyrin, tris (2-pyridylmethyl) amine, histidine, etc .;

(3) a compound having a carbonyl group having 1 to 3 or more carbonyl groups and 3 to 40 or more carbon atoms (excluding carboxylic acid);

Acethyl acetate, acetylacetone (acac), 2,4-pentanedione, bis (acetylacetone), 3-methylpentane-2,4-dione, 1-phenyl-1,3-butanedione, 3-phenyl Nilpentane-1,2,4-dione, 1,3-diphenyl-1,1,3-propanedione, 1-phenyl-1,3,5-hexanetrione, 5,5 '— (1,2-ethanediyl Dinitrile) bis (1-phenyl-1,3-hexanedione), trifluoroacetylacetone, hexafluoroacetylacetone, benzyl, dibenzoylmethane, asparaginebenzoylacetone, tenitol Rifoloacetone, 4,4,1- (1,2-ethanediyldinitrile) bis (2-pentynone), dipivaloylmethane, etc .;

(4) carboxylic acids having 1 to 4 or more carboxylic acid groups and 2 to 20 or more carbon atoms;

Oxalic acid, malonic acid, salicylic acid, fluoric acid, nicotinic acid, picolinic acid, aspartic acid, benzoylpyruvic acid, ethylenediamine diacetate, tri-triacetate, N,-(2-hydroxyethyl) ethylene diamine Acetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, trans-1,2- (cyclohexanedinitrile port) tetraacetic acid, (1,2-ethanediyldinitrile port) ) Tetraacetic acid, ethylenediamine tetrapropionic acid, glycine, N-methylglycine, glycylglycine, dali-sylglycylglycylglycine, salicylideneglycine, iminonic acid, methyliminominodiacetic acid, N, N-getyldiselenocarbamic acid , Methionine, 13

Oral phosphorus, sarcosine, xanthic acid, etc .;

(5) oximes having 1 to 4 or more oxime groups and 2 to 20 or more carbon atoms;

Dimethyldalioxime, 3- (2-aminoethylimino) 1-2-butenonone oxime, 2-pyridylaldoxime, 3-phenylimino-2-butanone oxime, salicylaldehyde oxime, etc .;

(6) phenols having 1 to 4 or more phenols and 6 to 30 or more carbon atoms;

Catechol, 1,2-benzenediol, 1,3-bis [bis (2-pyridylethyl) aminomethyl] phenol, 2,6-bis [bis (2-pyridylethyl) aminomethyl] —4-phenol, 1-1 2-troso-2-naphthol, etc .;

(7) ether having 1 to 8 or more ether groups and 4 to 30 or more carbon atoms;

Tetrahydrofuran, 1,4-dioxane, tetrahydrofuran, 1,4,

Xycyclocyclodecane, 4,7,13,16-tetraoxa 1,10-diazacyclodecane, 4,7,13,18-tetraoxa 1,10-diazabicyclo [8,5,5] icosane, 2,3-b 1,4-, 7,10,13-Penoxyoxacyclopent-2-ene, 4,7,13,16,21-Penoxa-1,10-Diazapiciclo [8,5,5] Trichosan , Monensin, nigeridin, etc .;

(8) a sulfur compound having 1 to 4 or more sulfur atoms and 2 to 40 or more carbon atoms; 14

Getylditi talent rubamic acid, ethylthioglycolic acid, ethylenebisthiodalicolic acid, ethylenethiourea, phenyldithioacetic acid, dithiobenzoic acid, 1,2-aminoethanethiol, diphenylthiolrubazone, dimethyl sulfoxide, 2,4-pentanedithione, 2,2,7,7-tetramethyl-3,6-dithiaoctane, 21-imidazolidinthione, dimethyldithiol-rubanic acid, thiourea, cystine, maleonitriledithiol, 1,4,8,11-nitetrathiaundecane;

(9) An amide compound having 1 to 3 or more amide groups and 3 to 54 or more carbon atoms;

Diazoamide, N, N-dimethylacetoamide, N, N-dimethylformamide, hexamethylphosphoric triamide, diphenylphosphinamide, aminoethylamide, oxamide, valinomycin, phthalimide, succinimide, norinomycin;

(10) N-oxides having 1 to 3 or more N-oxide groups and 6 to 20 or more carbon atoms;

Picolin-N-oxide, apicolin-N-oxide, pyridine-N-oxide and the like;

(11) Others;

Nitrogen molecule, water, carbon monoxide, urea, salicylaldehyde, hydrogen N-ditrosophenylhydroxylaminate, etc .;

3) The following conjugated compounds having 2 to 10 or more unsaturated groups and 4 to 14 or more carbon atoms are listed.

1,5-cyclooctanegen (hereinafter co d), 1,3,5,7-cyclobutacutatetraene, cyclopentagenenyl, pentamethylcyclopentene genil, trobolone, 1,10-phenanthroline, etc .;

From the viewpoint of vinyl polymerizability, preferably halogen (fluorine, chlorine, bromine, iodine) Fifteen

It is a compound containing an ion and a phosphorus atom, particularly preferably an anion of an atom selected from chlorine, bromine and iodine, and a tertiary phosphine compound. In addition, as the combination, preferably, the metal element (d l) is selected from five-period VIII group elements, and the ligand of the anion or neutral molecule is preferably used.

(d 2) is octane genion and Z or a tertiary phosphine compound. A method for synthesizing the complex compound (d) is usually obtained by mixing a salt of (d1) (eg, a metal halide) and (d2) at room temperature. In some cases, a target complex compound is formed after another intermediate complex compound is formed. The salt of (d 1) and (d 2) may be mixed as they are, or after being dissolved in an aqueous solution / solvent solution, or may be mixed in an aqueous solvent solution. If necessary, it may be heated to 30 to 200 ° C. If substances to be removed are formed, they may be removed under reduced pressure. The produced (d) may be used as it is or as a crystal, purified and used. As the solvent used here, for example, an alcohol-based solvent

(Methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), amide solvents (N, N-dimethylformamide, N-methylpyrrolidone, etc.), sulfoxide solvents (dimethyl sulfoxide, etc.), Mixtures of the above species can be given.

(d) has a very large number of compounds, but individual synthesis methods are, for example, Ange.Chem.Int.Ed.Engl., 12,57 (l973); J.Chem.Educ., 50,343 (l973); Accts. Chem. Rsearch, 3,105 (l970); Chm. Rev., 73,487 (l973); Interscience-Wilry (l968); Chem. Soc. Rev., 4, 27 (1975); Basic inorganic chemistry (F.A. Cotton, G. ゥ co-authored by Lilkinson, Baifukan); Inorganic compounds · Complex dictionary (Katsuyoshi Nakahara, Kodansha), etc.

The form of the coordination is not particularly limited, and may be terminal coordination (for example, triphenylphosphine as a ligand), bidentate (for example, ethylenediamine as a ligand), or multidentate (coordination) having 3 to 6-coordinates. The ligand is, for example, terpyridine. 16

They take the form of a complex coordination. Further, (d) is usually a non-electrolyte complex compound having no charge, but may be an electrolyte complex compound such as a complex cation or a complex anion having a charge.

Specific examples of (d) include the following.

As a specific example,

(1) When (d 1) is a Group IB metal element

〖Cu (CH ₃ ) (PPh ₃ )], [Cu ₂ Cl (cod) ₂ ] [Ag (py) ₂ ] CL [Ag (py) ₄ ] CL [Ag (py) ₄ ] Cl ₂ , [AuCl ( PPh ₃ )], [AuCl ₃ (PPh ₃ )], [Au (dppe)] Cl, etc .;

(2) When (d 1) is a 4-period Group VIII metal element

[FeCl ₂ (bpy) ₂ ], [FeCl ₂ (bpy) ₂ ] CL [FeCl (H) (CO) (PPh ₃ ) ₃ ], [FeCl (H) (dppe) ₂ ], [FeCl ₃ (NO) (PPh ₃ ) ₂ ], [FeCl ₂ (PPh ₃ ) ₃ ], [FeCl ₂ (PPh ₃ ) ₄ ], [Fe (CN) ₂ (bpy) ₂ ], [Fe (CO) ₂ (PPh ₃ ) ₃ ], [Fe (H) ₂ (N ₂ ) (PPh ₃ ) ₃ ], [Co ₂ CI ₂ (cod) ₂ ], [CoCl (CO) (PPh ₃ ) ₂ ], [CoCl (PPh ₃ ) ₃ ] , [CoCl (0 ₂ ) (PPh ₃ ) ₃ ], [CoCl ₃ (py) ₃ ], [Co (cod) ₂ ] Cl, [Co (H) (CO) (PPh ₃ ) ₃ ] [Ni (acac ) Cl (PPh ₃ )], [NiBr (CH ₃ ) {P (C 2H5) ₃ } ₂ ], [NiBr (NH ₃ ) ₃ ], [Ni (CH ₃ ) Cl (cod)], [Ni (C _{_{2 H 5) (cod)]}} CL [Ni (CH 3) (PPh 3)], [Ni 2 Cl 2 (acac) 2], [NiCl 2 (bpy)], [NiCl 2 (cod)], [Ni ₂ Cl ₂ (dppm)], [NiCl ₂ (en)], [NiCl ₂ (NH ₃ ) (PPh ₃ )] [NiCl ₂ (PPh ₃ )] [Ni ₂ Cl ₄ (PPh ₃ ) ₂ ], [Ni _{(PPh 3) J, [Ni} (py) 4] Cl 2, [Ni (SO 3) (H 2 O) 3], [Ni (S0 3) (NH 3) 3] and the like;

(3) When (d 1) is a Group VIII metal element with 5 periods

[Rh ₂ Cl ₂ (cod) ₂ ] [RhCl (CO) (PPh ₃ ) ₂ ]> [RhCl (PPh ₃ ) ₃ ], [RhCl (0 ₂ ) (PPh ₃ ) ₃ ], [RhCl ₃ (py) ₃ ], [Rh (cod) ₂ ] CL [Rh (H) (CO) (PPh ₃ ) ₃ ], [RuCl ₂ (bpy) ₂ ], [RuCl ₂ (bpy) ₂ ] CL [RuCl (H) ( CO) (PPh ₃ ) ₃ ], [RuCl (H) (dppe) ₂ ] [RuCl ₃ (NO) (PPh ₃ ) ₂ ], [RuCl ₂ (PPh ₃ ) ₃ ], [RuCl ₂ (PPh ₃ ) J , [Ru (CN) ₂ (bpy) ₂ ], [u (CO) ₂ (PPh ₃ ) ₃ ], [Ru (H) ₂ (N ₂ ) (PPh ₃ ) ₃ ], [Pd (acac) Cl ( PPh ₃ )], [PdBr (CH ₃ ) {P (C ₂ H ₅ ) ₃ } ₂ ], [PdBr (NH ₃ ) ₃ ], [Pd (CH ₃ ) Cl (cod)], [Pd (C ₂ H ₅ ) (cod)] CL [Pd (CH ₃ ) (PPh ₃ )], [Pd ₂ Cl ₂ (acac) ₂ ], [PdCl ₂ (bpy)], [PdCl ₂ (cod)], [Pd ₂ Cl 17

₂ (dppm)], [PdCl ₂ (en)], [PdCl ₂ (NH ₃ ) (PPh ₃ )], [PdCl ₂ (PPh ₃ )], [Pd ₂ Cl ₄ (PPh ₃ ) ₂ ], [Pd ( _{PPh 3) J, [Pd (} py) 4] Cl 2, [Pd (S0 3) (H 2 0) 3] [Pd (S0 3) (NH

3) 3] etc.;

(4) When (d 1) is a Group VIII metal element with six periods

[OsCl ₂ (bpy) ₂ ] [OsCl ₂ (bpy) ₂ ] CL [OsCl (H) (CO) (PPh ₃ ) ₃ ], [OsCl (H) (dppe) ₂ ], [OsCl ₃ (NO) ( PPh ₃ ) ₂ ]> [OsCl ₂ (PPh ₃ ) ₃ ], [OsCl ₂ (PPh ₃ ) ₄ ], [Os (CN) ₂ (bpy) J, [Os (CO) ₂ (PPh 3) 3], [Os (H) ₂ (N ₂ ) (PPh ₃ ) ₃ ], [Ir ₂ CI ₂ (cod) ₂ ], [IrCl (CO) (PPh ₃ ) ₂ ], [IrCKPPh ₃ ) ₃ ], [IrCl ( 0 ₂ ) (PPh ₃ ) ₃ ], [IrCl ₃ (py) ₃ ], [Ir (cod) ₂ ] CL [Ir (H) (CO) (PPh ₃ ) ₃ ], [Pt (acac) Cl (PPh ₃ )], [PtBr (CH ₃ ) {P (C ₂ H ₅ ) ₃ } ₂ ], [PtBr (NH ₃ ) ₃ ], [Pt (CH ₃ ) Cl (cod)], [Pt (C ₂ H ₅ ) (cod)] Cl, [Pt (CH ₃ ) (PPh ₃ )], [Pt ₂ Cl ₂ (acac) ₂ ], [PtCl ₂ (bpy)], [PtCl ₂ (cod)], [Pt ₂ Cl ₂ (dppm)], [PtCl ₂ (en)], [PtCl ₂ (NH ₃ ) (PPh ₃ )], [PtCl ₂ (PPh ₃ )], [Pt ₂ Cl ₄ (PPh ₃ ) ₂ ]> [ _{Pt (PPh 3) J [Pt} (py) 4] Cl 2, [Pt (S0 3) (H 2 0) 3], [Pt (S0 3) (NH 3) 3] , and the like; and others as mentioned, Without particular limitation, the compounds in the above ranges can be applied. Preferably, [RuCl ₂ (PPh ₃ ) ₃ ], [RuCl ₂ (PPh ₃ ) ₄ ]> [Pd ₂ CI ₂ (dppm)], [RhCl (CO) (PPh ₃ ) ₂ ], [RhCl (PPh ₃ 5) Group VIII metal elements (ruthenium, rhodium, palladium), such as ₃ ], anions of atoms selected from chlorine, bromine and iodine, and coordination selected from the group consisting of tertiary phosphine compounds It is a complex compound that has

Further, from the viewpoints of polymerizability and operability, (d) is preferably a complex compound soluble in water or a water-soluble organic solvent. Examples of the water-soluble organic solvent include the same ones used when synthesizing the above (d).

Preferably, based on the weight of (d) and (dl) or the total weight of monomer and first crosslinking agent, the amount of (d) is from 0.005 ppm to 2.0% by weight, (d 1 ) Is 0.001 ppm to 1.0 mass%, more preferably the amount of (d) is 0.01 ppm to 1.0 mass%, and the amount of (dl) is 0.1 mass%. 005 p pm to 0. 18

5% by weight, particularly preferably the amount of (d) is from 0.02 ppm to 0.6% by weight, and the amount of (dl) is from 0.01 ppm to 0.3% by weight.

When the amount of (d) is 0.0005 111 to 2% by mass and the amount of (dl) is 0.001 lp pm to 1% by mass, the polymer exhibits the performance as an absorbent article and the polymerizable monomer. The polymerization rate and the polymerization rate are also sufficient, and the productivity is good.

When the solubility of (d) in the aqueous polymerization solution is low, the polymerization may be carried out by dissolving or dispersing the monomer in the aqueous polymerization solution together with a water-soluble organic solvent, a surfactant and the like.

The water-absorbent resin (A) obtained by the above method is optionally used in the form of a hydrogel to form the crosslinking agent (a-2) or a polyvalent metal compound capable of forming ionic crosslinking (calcium chloride, magnesium sulfate, sulfuric acid) Aluminum, etc.) can be further bridged. As a result, relatively uniform crosslinking is achieved, and a water-absorbent resin having a high gel strength and a small amount of water-soluble components can be produced.

The water-containing gel-like polymer of the absorbent resin obtained in this way is dried, pulverized and, if necessary, adjusted in particle size. The surface of the cross-linked polymer obtained is cross-linked with a cross-linking agent (second cross-linking agent). The effect of the present invention can be further improved by using the absorbent resin (A) described above.

The drying method is a method of drying with hot air at a temperature of 80 to 230 ° C, a thin film drying method using a drum dryer heated to 100 to 230 ° C, (heating) a reduced pressure drying method, a freeze drying method. An ordinary method such as a drying method using infrared rays may be used. There is no particular limitation on the pulverizing method, and ordinary equipment such as a hammer type pulverizer, an impact type pulverizer, a roll type pulverizer, and a jet stream type pulverizer can be used. The obtained ground material is sieved as necessary to adjust the particle size. The shape of the crosslinked polymer after pulverization is not particularly limited, and examples thereof include irregularly pulverized, scaly, pearl, rice, and granulated forms. The irregularly crushed shape is preferred in that it is well entangled with fibrous materials for use in disposable diapers and there is no fear of falling off from the fibrous materials. 19

The obtained particulate water-absorbent resin (A) is sieved, if necessary, to adjust the particle size. The mass average particle diameter of the obtained (A) is preferably 100 to 800 / im, more preferably 200 to 500 m, and particles in the range of 100 to 850 m become 95% by mass or more. What was crushed as described above can be used. The content of fine particles is preferably small, and the content of particles of 100 / im or less is preferably 3% or less, more preferably the content of particles of 150 m or less is 3% or less. The mass average particle diameter is obtained by plotting each particle size distribution of the water-absorbent resin on the horizontal axis with the particle diameter, and the vertical axis on the log-probability paper of the mass-based content, and occupying 50% of the total mass. It depends on the method of finding.

As a method for surface-crosslinking the water-absorbent resin (A), a conventionally known method, for example, a mixed solution of a second crosslinking agent (a-3), water and an organic solvent is mixed with (A) and heated. A method for causing the reaction is mentioned.

(a-3) may be the same as or different from (a-2), but is preferably a functional group capable of reacting with an acid group such as a carboxyl group of (m) and / or its base. It is a crosslinking agent having at least two groups, and particularly preferably a polydaricidyl ether compound such as ethylene darico-ludaridicyl ether, a polyamine resin and an aziridine compound in that surface crosslinking can be performed at a relatively low temperature. It is.

The amount of (a-3) used is preferably 0.001 to 7.0% by mass, more preferably 0. 0% based on the total mass of (a-1) (a-2) and (a-3). 0.02 to 5.0% by mass, particularly preferably 0.003 to 4.0% by mass. When the amount of (a-3) is 0.001% by mass or more, the degree of surface cross-linking is sufficient, and the effect of improving the absorption under load is also sufficient. On the other hand, when the amount of (a_3) used is 7.0% by mass or less, the degree of cross-linking on the surface is not excessive and the amount of water retention does not decrease.

The amount of water used during surface mounting is preferably based on the mass of the water-absorbent resin (A). 20

It is preferably 1 to 10%, more preferably 2 to 7%. When the amount of water used is 1% or more, the penetration of the water-absorbent resin (A) of (a-3) into the particles becomes sufficient, and the amount of water absorbed under the load, particularly under a high load (for example, 60 g / cm ² ), the effect of improving the absorption is good. On the other hand, if your water usage is less than 10%,

(a-3) The penetration of (A) into the interior does not become excessive, and the amount of absorption under load is improved. Therefore, the problem that water retention and blood retention greatly decrease does not occur. In the present invention, as the kind of the organic solvent used in combination with water, a conventionally known hydrophilic solvent can be used, and the degree of penetration into (A) of (a_3) (A),

It can be appropriately selected in consideration of the reactivity of (a-3) and the like. Preferred are water-soluble hydrophilic organic solvents such as methanol and diethylene glycol. Such solvents may be used alone or in combination of two or more. The amount of the solvent used can be variously changed depending on the type of the solvent, but is preferably 1 to 10% based on the mass of (A). Also, the ratio of the solvent to water can be arbitrarily changed, and is preferably 20 to 80%, more preferably 30 to 70% by mass.

A mixed solution of (a-3), water and a solvent is added to and mixed with (a2) by a conventionally known method, and a heating reaction is performed. The reaction temperature is preferably from 80 to 200 ° (and more preferably from 100 to 160 ° C. The reaction time can be varied depending on the reaction temperature, but is preferably from 3 to 60 minutes, More preferably, it is 5 to 40 minutes.

It is also possible to subject the particulate water-absorbent resin (A) obtained by surface cross-linking to additional surface cross-linking with the same (a-13) or different (a-3). The particulate water-absorbent resin (A) thus obtained is sieved as necessary to adjust the particle size. The mass average particle diameter of the obtained (A) is almost the same as before the surface cross-linking, preferably 100 to 800 m, more preferably 200 to 500 m, and particles in the range of 100 to 850 m account for 95% by mass or more. Powder so that twenty one

Crushed ones can be used. The content of the fine particles is preferably small, and the content of the particles having a particle size of 100 m or less is preferably 3% or less, and more preferably the content of the particles having a particle size of 150 m or less is 3% or less.

Such a surface crosslinked type crosslinked copolymer is preferable because it has excellent absorption performance not only under normal pressure but also under a load, and has a high gel strength.

The average particle diameter of the water-insoluble non-porous spherical single particles (B) having an average particle diameter of 1 to 50 nm used in the present invention is preferably 3 to 40 nm, more preferably 5 to 35 nm. Particularly preferably, it is 10 to 30 nm.

If the average particle diameter is less than 1 nm, the resulting absorbent will have a poor diffusion and absorption rate of the liquid into the resin. Further, even if the thickness exceeds 50 nm, the absorption and diffusion rate of the liquid into the resin of the obtained absorbent becomes poor. The average particle diameter can be measured by a usual method, for example, a calculation from a value obtained by a BET method, a Sears method, a laser method, or the like.

(B) is a non-porous spherical single particle. Porous particles have poor diffusion and absorption rates. The shape is spherical. Shapes other than spherical, such as hollow, porous, petal, agglomerated, and granulated, pose problems in handling. The fact that (B) is spherical can be confirmed, for example, by observing particles in a dispersed state under conditions of an acceleration voltage of 100 KV using a transmission electron microscope (for example, model H-710 OFA manufactured by Hitachi, Ltd.). I understand. Further, (B) has a preferable specific surface area from the viewpoint of improving the diffusion absorption rate, and is 50 to 40 On ^ Zg. More preferably from 75~35 OmVg, particularly preferably 1 00~300m ² Zg. The specific surface area can be measured by a BET method, a Blaine method, or the like. For a sphere, for example, the specific surface area is determined assuming a single particle sphere from the average particle diameter determined by a measurement method other than the BET method, and the sphericity can be determined by comparing this value with the specific surface area measured by the BET method. The specific surface area (i) calculated from the average particle diameter of the particles of the present invention is close to the measured value of the specific surface area (ii) by the BET method. The value of (i) is preferably 90 to 110% of (ii). twenty two

When single particles are aggregated, a space is created between the aggregated particles and the state becomes the same as that of the porous particles, the average particle diameter increases, and the specific surface area decreases. Therefore, the abundance ratio of single particles (primary particles) and aggregated particles (secondary particles) can be controlled by the average particle diameter and the specific surface area. AEROSIL 200 (silica manufactured by Nippon AEROSIL) has primary particles of 60 nm or less, but does not disperse in primary particles even if aggregated and dispersed or solubilized in water, and the average particle diameter is usually 100 nm. It is not used in the present application because it is not less than nm. This is presumed to be due to the fact that the primary particles agglomerated in the drying step in the particle manufacturing method are hard to return to the original primary particles even when dispersed in water. It is important that the primary particles are not dried before use.

The type of material (B) is not particularly limited as long as it has an average particle size of 1 to 50 nm, is insoluble in water and is nonporous, and may be any of an organic or inorganic material. .

Examples of organic non-porous spherical single particles include, for example,

(i) Organic non-porous spherical single particles consisting only of carbon atoms; polyethylene, polypropylene, polystyrene, poly-p-xylylene, polybutadiene, etc.

(ii) Organic nonporous spherical single particles composed of carbon and oxygen atoms; polyacrylate, polymethacrylate, polyvinyl acetate, polyvinyl ether, thermoplastic polyester, polycarbonate, polyphenylene oxide, polyepoxy, polyacetal, cellulose Derivatives, etc.

(m) Organic non-porous spherical single particles containing nitrogen atoms; polyacrylonitrile, polyamide, thermoplastic polyurethane, etc.

(iv) Other organic nonporous spherical single particles; polyvinyl chloride, polyvinylidene chloride, fluororesin, polysulfone, etc., and those obtained by copolymerizing two or more kinds of monomers constituting these resins. No. Preferably (i). In addition, when the hydrogel is dried, the organic nonporous spherical single particles do not melt, so that the gel needs to have a melting temperature higher than the drying temperature. It is the balance with the drying temperature, twenty three

The melting temperature of the organic non-porous spherical single particles is usually 13 Ot or more, preferably 150 ° C or more.

The inorganic non-porous spherical single particles may be either a natural inorganic substance or a synthetic inorganic substance, and examples thereof include oxides such as silicon oxide, aluminum oxide, iron oxide, titanium oxide, magnesium oxide, and zirconium oxide. . Two or more of these may be used in combination, or two or more of these may be combined.

Among them, preferred are inorganic non-porous spherical single particles, more preferred are silicon oxides, and particularly preferred are amorphous silicon oxides.

When (B) is used as a 10% by mass aqueous dispersion or water solubilizing solution, the pH is not particularly limited, but it is said that the PH is stably present as primary particles, and that secondary aggregates are not formed. From the viewpoint, it is usually 2 to 11, preferably 2.5 to 10.

The amount of the non-porous spherical single particles (B) with respect to the water-absorbent resin (A) is preferably 0.01 to 5.0% by mass, more preferably 0.02 to 3.0% by mass, especially Preferably it is 0.04 to 2.5% by mass. When the amount of (B) added is at least 0.01% by mass, the effect of improving the rate of diffusion and absorption into the resin can be seen. On the other hand, when the mass is 5.0% or less, the diffusion absorption rate can be improved, and the mechanical strength of the obtained absorbent particles is high. Furthermore, the absorption capacity, water retention Z blood retention amount and pressure absorption amount of the obtained absorbent do not decrease.

(B) is mixed with (A). It may be blended at any stage from the polymerization in the production of (A) to before and after drying.

(i) When blended before drying, it may be added to the polymerization solution and polymerized, and a mixture of (A) and the hydrogel polymer (B) may be blended. (B) may be added to the mixture to form a mixture. The mixing may be carried out in a usual mixing apparatus described later, and there is no problem if the mixing temperature is from the polymerization temperature to room temperature. The mixing time is twenty four

Preferably, it is 30 minutes to 5 hours.

In this case, since the non-porous spherical single particles are mixed in the hydrogel state, the non-porous spherical single particles are then contained (incorporated) in the resin by evaporating the water in the hydrogel. Thereby, the diffusion and absorption speed of the liquid into the resin is improved.

(ii) When (B) is blended after drying, non-porous spherical single particles cover the particle surface of (A), or (A) and non-porous spherical single particles are separated and mixed as a mere mixture of both. It will be. In this case, in addition to preventing the phenomenon that (A) associates with each other via water, in the case of the liquid to be absorbed containing water-insoluble and hardly water-soluble components, these will cover the surface of (A) and reduce the performance It has the effect of preventing. This is thought to be the same as the principle of using a filter aid to prevent clogging when filtering using a filter.

The methods (i) and (ii) may be used in combination. Of these methods, the method (ii) is preferred.

(B) is a single particle state, that is, a non-aggregated state, and it is preferable that the aqueous dispersion, emulsion or water-solubilized state of (B) is mixed with (A). Particularly preferred is a method in which the water-solubilized product of (B) is mixed with (A). Water solubilization is because secondary particles are easily dispersed in primary particles. The solubilized state refers to a phenomenon in which a substance that is insoluble in the solvent appears to be dissolved, and can be visually judged. The solubilized state includes a colloidal state. The solubilized state can be measured by transmittance, and the transmittance is preferably 80% or more, more preferably 90% or more. Transmittance can be measured with a spectrophotometer. The aqueous dispersion or water-solubilized product can be mixed with a conventional mixing device, but it is important that the particles are not dried from the time they are manufactured until they are used. This is because once dried particles become aggregated particles and are not easily redispersed in water. The solid content concentration is preferably from 1 to 50% by mass, and more preferably from 5 to 35% by mass. The dispersion medium is preferably water, but if necessary, twenty five

A water-soluble solvent (an alcohol such as methanol or ethanol, a ketone such as acetone, or an ester such as ethyl acetate) may be used in combination at 70% by mass or less based on water. As a method of mixing, the water-solubilized substance of (B) is mixed with the dry powder particles of (A), or the water-solubilized substance of (B) is added after polymerization of (A) and before drying. And then heating and drying, but the former is preferred. When mixing using the second crosslinking agent, the dry powder particles (A) obtained by aqueous polymerization of the water-soluble monomer and the first crosslinking agent, the water-solubilized substance (B) and the second (Ii) a method of mixing the cross-linking agent at the same time and then drying by heating, or a method of mixing the dried powder particles of (A) and the second cross-linking agent and drying by heating and then mixing the water-solubilized product of (B). , Preferably the latter.

Further, the water content in the mixture of the water-containing gel (A) and (B) in the method (i) is not particularly limited, but is preferably 2 to 10 times the solid content of (A). It is. If it is twice or more, the uniformity at the time of kneading is large, and the effect of improving the diffusion absorption rate of the obtained absorbent is also good. If it is less than 10 times, the drying time is short, and it is economical.

A known device can be used as a mixing device for mixing (B) with (A) in a hydrogel state and uniformly mixing. Specific examples of the device include a double-arm kneader, an internal mixer (Banbari mixer), a self-cleaning mixer, a gear compounder, a screw-type extruder, a screw-type kneader, and a mincing machine. These can be used in combination of two or more.

The drying temperature of the hydrogel mixture to which (B) has been added is usually 60 to 230 ° (: preferably 100 to 200 °, particularly preferably 105 to 180 ° C). When the drying temperature is 60 ° C or higher, the drying time is short and economical, while when the drying temperature is 230 ° C or lower, there is no side reaction or decomposition of the resin, and the absorption performance and diffusion are improved. There is no decrease in absorption rate. 26

The device for drying the mixture of (A) and (B) in a hydrogel state may be a conventional device, such as a drum dryer, a parallel flow band dryer (tunnel dryer), a vent band dryer, and a jet flow (nozzle). Jet) dryer, box type hot air dryer, infrared dryer, etc. The heat source is not particularly limited. These dryers can be used in combination of two or more.

In the mixture of (A) and (B) of the present invention, if necessary, as an additive or a bulking agent, a residual monomer reducing agent (eg, sodium sulfite, hydrogen peroxide, etc.), a surfactant, an antibacterial agent (eg, Quaternary ammonium salt compounds, chlorhexidine compounds, metal salt antibacterial agents, etc.), preservatives, fragrances, deodorants, coloring agents, antioxidants, and fine fillers other than (B). Can be added. The amount of addition is preferably 0.1 to 50% by mass based on (A) + (B). These additives can also be added during or after the drying of the hydrogel mixture.

Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant, for example, those described in US Pat. Good.

Examples of the anionic surfactant include a hydrocarbon ether having 8 to 24 carbon atoms, rubonic acid or a salt thereof [oxyethylene (degree of polymerization = 1 to 100), lauryl sodium teracetate, and oxyethylene (degree of polymerization = 1 to 1). 00) Lauryl sulfosuccinic acid 2 sodium, etc.], C8-C24 hydrocarbon sulfate [Sodium lauryl sulfate, oxyethylene (degree of polymerization = 1-100) Sodium lauryl sulfate, oxyethylene (degree of polymerization = 1-100) Triethanolamine lauryl sulfate, oxyethylene (degree of polymerization = 1 to 100) coconut oil fatty acid sodium monoethanolamide sulfate], hydrocarbon sulfonate having 8 to 24 carbon atoms [such as sodium dodecylbenzene sulfonate] and carbon number 8 to 24 hydrocarbon phosphate salts (sodium lauryl phosphate, oxyethylene (polymerization degree = 1 to 100) Sodium Lil ether phosphate, etc.], fatty acid salts [La 27

ナトリウム Sodium phosphate, triethanolamine laurate, etc.], acylated amino acid salts [sodium methyltaurine coconut oil fatty acid, sarcosine sodium coconut oil fatty acid, sarcosine triethanolamine coconut oil fatty acid, N-coconut oil fatty acid acyl-L-glutamic acid Triethanolamine, N-coconut fatty acid acyl L-sodium glutamate, lauroylmethyl-jS-alanine sodium, etc., and others [oxyethylene sulfosuccinate (degree of polymerization = 1-100) sodium disodium propylethanolamide] And the like.

Specific examples of the nonionic surfactant include, for example, aliphatic alcohols (8 to 24 carbon atoms), alkylene oxides (2 to 8 carbon atoms), adducts (degree of polymerization = 1 to 100), and lauryl alcohol ethylene oxide. Addition (polymerization degree = 20), oleyl alcohol ethylene oxide addition (polymerization degree = 10), macco alcohol ethylene oxide addition (polymerization degree = 35), etc.), oxyalkylene (carbon number 2-8, polymerization) Degree = 1 to 100) Higher fatty acids (carbon number 8 to 24) Esters [polyethylene glycol monostearate (degree of polymerization = 20), polyethylene glycol distearate (degree of polymerization = 30), etc.], polyvalent (2 Valency ~ 10 valency or higher) Alcohol fatty acid (carbon number 8 ~ 24) ester [glyceryl monostearate, ethylene glycol monostearate, sorbitan diphosphate (mono) Z-diester, sorbitan palmitic acid (mono / di) ester, sorbitan stearic acid (mono / di) ester, sorbitan oleic acid (mono-Zdi) ester, sorbitan palm oil (mono-Zdi) ester, etc.] , Polyoxyalkylene (C2-8, degree of polymerization = 1-100) Polyhydric (divalent-10 or more) Alcohol higher fatty acid (C8-24) Ester [polyoxyethylene (degree of polymerization Sorbitan lauric acid (mononodi) ester, polyoxyethylene (degree of polymerization = 20) sorbitan palmitic acid (mono / di) ester, polyoxyethylene (degree of polymerization = 15) sorbitan stearate (mono-Z ) Ester, polyoxyethylene (degree of polymerization = 10) sorbita 28

Oleic acid (mono-Z di) ester, polyoxyethylene (degree of polymerization = 25) Lauric acid (mono-Z di) ester, polyoxyethylene (degree of polymerization = 50) stearic acid (mononodi) ester, polyoxyethylene (degree of polymerization = 1 8) Oleic acid (mononodi) ester, sorbitan, polyoxyethylene (degree of polymerization = 50) methyl dalcoside dioleate, etc.], fatty acid alkanolamide [1: 1 type coconut oil fatty acid diethanolamide, 1: 1 type] Lauric acid diethanolamide, etc.), polyoxyalkylene (C2-8, degree of polymerization = 1-100) Alkyl (C1-22) phenyl ether (polyoxyethylene (degree of polymerization = 20) nonylphenyl Ether, etc.), polyoxyalkylene (2-8 carbon atoms, degree of polymerization = 1-100) alkyl (8-24 carbon atoms) aminoether and alkyl ( C8-C24) Dialkyl (C1-C6) Aminoxide [radiyl dimethyl amine oxide, etc.], polydimethylsiloxane ethylene oxide adduct, polyoxyethylene / polyoxypropylene block polymer (weight average) Molecular weight = 150-10000).

Examples of the cationic surfactant include a quaternary ammonium salt type [stearyltrimethylammonium chloride, benzyltrimethylammonium chloride, distearyldimethylammonium chloride, and lanolin fatty acid aminopropyl fatty acid aminopropyldimethylammonium chloride. And the like, and amine salt types [eg, acetylaminoethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.] and the like.

Examples of the amphoteric surfactant include betaine-type amphoteric surfactants [cocopropyl fatty acid amidopropyldimethylaminoacetic acid, lauryldimethylaminoacetic acid, 2-alkyl-N-hydroxypropyl-N-hydroxyethylamine]. Louisimida zolinidumbetaine, laurylhydroxysulfobetaine, lauroylamidoethylhydroxyethylcarboxymethylbetaine sodium hydroxypropylphosphate, etc.], amphoteric amino acid surfactant [j6-laurylaminopropiate] 29

Sodium onoate].

Antioxidants include triethyleneglycol-l-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5 —Di-tert-butyl 4-hydroxyphenyl) propionate], octyl decyl 3- (3,5-di-tert-butyl-14-hydroxyethoxyphenylpropionate, 3,5-di-tert-butyl-41-hydroxybenzylphosphonate— Hindered phenol-based antioxidants such as getyl ester; and amine-based antioxidants such as n-butylamine, triethylamine, and cetylaminomethyl methacrylate.

UV absorbers include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl_2-hydroxyphenyl) benzotriazole, 2_ (3, Benzotriazoles such as 5-di-tert-butyl_2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl 2-hydroxyphenyl) benzotriazole UV absorber; 2 — (4,6-diphenyl 1,3,5 —triazine-1 21) 1-5 — [(hexyl) oxy] triazine ultraviolet absorber such as phenol; 2 Benzophenone-based ultraviolet absorbers such as hydroxy-4-n-octyloxybenzophenone; oxalic acid-based ultraviolet absorbers such as 2-ethoxy-2'-ethyloxalic acid bisanilide; Combined use of more than one species It is.

Inorganic powders include calcium carbonate, kaolin, talc, myriki, bentonite, clay, sericite, asbestos, glass fiber, carbon fiber, glass powder, glass balloon, shirasu balloon, coal powder, metal powder, and ceramic powder. , Silica, zeolite, slate powder and the like. The form may be arbitrary, and the average particle size is preferably from 0.1 micron to 1 mm.

As pigments, for example, carbon black, titanium oxide, red iron oxide, lead red, 30

Para red, navy blue and the like.

Examples of organic fibrous materials include natural fibers (cellulosic (cotton, sawdust, straw, etc.) and others, peat, wool, microfibrils, bacterial cellulose, etc.), and artificial fibers (cellulose such as rayon, acetate, etc.). Etc.), synthetic fibers (polyamide, polyester, acrylic, etc.), pulp [mechanical pulp (crushed wood pulp from logs, asplund crushed wood pulp, etc.), chemical pulp (sulfurous pulp, soda pulp, sulfate pulp, etc.) Nitric acid pulp, chlorine pulp, etc., semi-chemical pulp, recycled pulp (for example, mechanically crushed or crushed paper made from pulp once, or recycled pulp that is mechanically crushed or crushed paper) )] And the like.

The absorbent of the present invention has a diffusion and absorption rate of 25 to 65 mlZg, preferably 28 to 60 m1Zg, for bovine blood (containing 3.8% of citric acid: hemato value = 20% by volume). When used for sanitary products such as napkins, it is effective for improving dry feeling and reducing leakage. In addition, the absorbent of the present invention obtained by surface cross-linking has an improved initial pressure absorption amount, a diffusion absorption rate for bovine blood of 25 to 65 mlZg, preferably 28 to 60 ml / g, and an initial pressure absorption for bovine blood. By adjusting the amount to 18 to 40 gZg, preferably 25 to 40 g / g, the quality of dryness and the feeling of dryness used in sanitary goods such as disposable diapers and napkins are further improved, and leakage can be further reduced and more effective It is a target. In addition, physiological saline has excellent diffusion absorption rate, initial pressure absorption amount, and water retention amount. The hematoma of the bovine blood used can be adjusted using physiological saline or plasma. Also, the values may vary slightly depending on the bovine blood used, but it is possible to determine the superiority of the absorbent.

(Absorbent structure, absorbent article)

The absorbent (C) of the present invention has remarkably excellent absorption characteristics such as diffusion absorption rate and absorption amount. 31

Thus, by applying to various absorbent structures (F) and absorbent articles, articles having excellent absorbent performance can be obtained.

The method of applying the water-absorbing agent (C) of the present invention to the absorbent structure (F) is, for example, a method comprising a matrix of (C) and a fibrous material (E).

(1) Spray (C) between layers of fibrous material composed of pulp, heat-fusible fibers, etc. arranged in layers;

(2) mixing fibrous material such as pulp and heat-fusible fiber with (C);

(3) Absorbent structures made of a non-woven fabric of two or more gouges and a nonwoven fabric, if necessary, by a method of sandwiching (C) together with a fibrous material.

Examples of (E) include fibrous materials conventionally used in absorbent articles, such as various fluff pulp and cotton-like pulp. Pulp, Chemi-thermomechanical pulp (CTMP), etc.], and bleaching method are not particularly limited.

As the fibrous material, in addition to the above-mentioned organic fibrous material, if necessary, synthetic fibers that do not swell in water can be used alone or in combination with the fluff pulp, the cotton pulp, or the like. Examples of the synthetic fibers include polyolefin fibers (for example, polyethylene fibers, polypropylene fibers, polyester fibers (for example, polyethylene terephthalate fibers), polyolefin 'polyester composite fibers, polyamide fibers, and polyacrylonitrile fibers. .

The length and thickness of (E) are not particularly limited, and usually, the length is preferably 1 to 200 mm, and the thickness is preferably 0.1 to 100 denier. The shape is not particularly limited as long as it is a fiber shape, and examples thereof include a web shape, a thin cylindrical shape, a cut split yarn shape, a stable shape, and a filament shape.

The amount of the absorbent (C) of the present invention added to the absorbent structure (F) can be varied depending on the type and size of the absorbent structure and the target absorption performance. 32

However, the amount of (C) is preferably from 30 to 95% by weight, more preferably from 40 to 95% by weight, based on the mass of (F).

The absorbent article of the present invention is preferably an absorbent article provided with an absorbent structure (F), a liquid-permeable sheet, and a breathable back sheet, and more preferably an absorbent article as a sanitary article. Examples of hygiene products include disposable diapers (child diapers, adult disposable diapers, etc.), napkins (sanitary napkins, etc.), paper napkins, pads (pads for incontinent persons, surgical underpads, etc.), pet sheets (ぺUrine absorbing sheet). Preferred are napkins and disposable diapers.

Example

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The diffusion absorption rate, initial pressure absorption amount, pressure absorption amount and water retention of the obtained absorbent were measured by the following methods. Hereinafter, unless otherwise specified,% indicates mass%.

[Measuring method of diffusion absorption rate]

0.10 g of an absorbent adjusted to a particle size of 30 to 60 mesh with a JIS standard sieve is prepared as a sample.

Set the device shown in Figure 1 on a horizontal table. In addition, confirm that the position of the capillary 5 which is the air inlet and the upper surface of the flat plate 6 are horizontal.

Close the cock 1 at the bottom of the burette and the cock 2 in the side hole, and put bovine blood (3.8% citric acid content: hemato value = 20% by volume: manufactured by Towa Junyaku) in the burette 4 from the top of the burette. Put in. Next, close the top of the burette with the rubber stopper 3 and read the scale indicating the volume of bovine blood in the burette before opening the bottom cock 1 and the side hole cock 2. A plain weave nylon mesh (5 cm x 5 cm) 7 with an aperture of 63 / m is spread over the hole of the flat plate 6 with a hole of 3 mm, and 0.10 g of the sample 8 is put on the mesh. Absorption starts when the sample is placed, but from this point onwards 33

Start the measurement and measure the absorption 2 minutes later by reading the scale of the bullet. The diffuse absorption amount is 10 times the volume of bovine blood in the burette that has been sucked and reduced.

[Measuring method of initial pressure absorption and pressure absorption]

Cylindrical plastic tube with 250 mesh nylon mesh stuck on the bottom

0.10 g of an absorbent sample adjusted to a particle size of 30 to 60 mesh with a JIS standard sieve is placed within (inner diameter Φ 30 mm, height 60 mm) and leveled evenly. A weight having an outer diameter of Φ30 mm and a load of 20 gZcm ² is placed on the absorbent. At the center of a petri dish (diameter ψ12 cm) containing 60 ml of bovine blood, place a plastic tube containing the absorbent with the nylon mesh side facing down. The increased mass of the bovine blood absorbed by the absorbent is measured after 10 and 60 minutes. The 10-fold increase in weight after 5 minutes is the initial pressure absorption for bovine blood, and the 10-fold increase in weight after 60 minutes is the pressure absorption for bovine blood.

[Method of measuring blood retention]

A 1.00 g absorbent sample adjusted to a particle size of 30 to 60 mesh with a JIS standard sieve is placed in a tea bag (20 cm long, 10 cm wide) made of 250 mesh nylon mesh, and 500 ml of bovine blood After immersion in water for 60 minutes to absorb, suspend for 15 minutes to drain, and then centrifuge with a centrifuge at 150 G for 90 seconds to measure the increased mass and preserve it against bovine blood. Blood volume. Example 1

In a 1-liter glass reaction vessel, 77 g of sodium acrylate, 22.8 g of acrylic acid, 0.2 g of N, N'-methylenebisacrylamide, 395 g of deionized water and dicrotoritol (triff) (Enylphosphine) Ruthenium (0.00 lg) was charged, and the temperature of the contents was maintained at 3 ° C. while stirring and mixing. After injecting nitrogen into the contents to reduce the amount of dissolved oxygen to 1 ppm or less, hydrogen peroxide 34

1% aqueous solution of lg, 1.2 g of a 0.2% aqueous solution of ascorbic acid and 2.8 g of a 2% aqueous solution of 2,2'-azobisamidinopropane dihydrochloride are added and mixed to initiate polymerization. After about 5 hours of polymerization, a water-containing gel-like water-absorbent resin (A1) was obtained. (A1) is shredded to a size of 2 to 5 mm with an internal mixer. Ethylene glycol diglycidyl ether 0.1 lg and a non-porous spherical amorphous silicon oxide colloid aqueous solution manufactured by Clariant Japan KK Kurepozo Ichiru 30H25 (10% aqueous dispersion of pH = 2. 5, the average particle diameter = 25 nm, specific surface area = 120 m ² / g, solid content 30%) (B 1) was lg added pressure, further in evening After mixing uniformly with a single mixer, the mixture was dried with a ventilated band dryer (manufactured by Inoue Metal Industry) at 150 ° C and a wind speed of 2. OmZ seconds.

The obtained dried product was pulverized and adjusted to a particle size of 20 to 100 mesh to obtain an absorbent (1). Table 1 shows the performance evaluation results of the absorbent (1). Example 2

The hydrogel water-absorbent resin (A1) obtained in Example 1 was shredded to a size of 2 to 5 mm with an internal mixer, 0.1 g of ethylene glycol diglycidyl ether was added, and further the internal mixer was used. After uniform mixing, the mixture was dried with a ventilation band dryer (manufactured by Inoue Metal Industry) at 150 ° C and a wind speed of 2. OmZ seconds. The obtained dried product was powder-framed and adjusted to a particle size of 20 to 100 mesh. Next, 1 g of (B1) was added to the mixture, and the mixture was further uniformly mixed with an internal mixer, and then adjusted to a particle size of 20 to 100 mesh to obtain an absorbent (2). Table 1 shows the performance evaluation results of the absorbent (2). Example 3

The hydrogel water-absorbent resin (A1) obtained in Example 1 was shredded to a size of 2 to 5 mm with an internal mixer, and the same amount of (B1) as in Example 1 was added and mixed. 35

Next, an absorbent having a particle size of 20 to 100 mesh was obtained in the same manner as in Example 1. While 100 g of this absorbent was stirred at a high speed, 2 g of a 1% water / methanol mixed solution of ethylene glycol diglycidyl ether (water / methanol = 30/70) was added and mixed, followed by heat crosslinking at 140 ° C for 30 minutes. As a result, a surface cross-linking type absorbent (3) was obtained. Table 1 shows the performance evaluation results of the absorbent (3). Examples 4 and 5

In Example 2, a surface-crosslinked absorbent (4) and an absorbent (5) were used in the same manner as in Example 1 except that 0.5 g or 3 g was used instead of 1 g of (B1). ). Table 1 shows the performance evaluation results. Examples 6, 7

In Example 2, an absorbent (6) was prepared in the same manner as in Example 2 except that the following nonporous spherical single particles (B2) or (B3) were used in the same amounts instead of (B1). And an absorbent (7). Table 1 shows the performance evaluation results of these absorbents.

(B 2): Clarisol Japan Co., Ltd. Crevosol 30 CAL 25

(PH of 4.0% aqueous dispersion = 4.0, average particle size = 25 nm, specific surface area = 200 m ² / g, solid content 30%)

(B3): Clariant Japan Co., Ltd. Creposol 30 R 9

(1 0% aqueous dispersion of pH = l 0. 7, the average particle size = 9 nm, specific surface area = 300 meters ² Zg, 30% solids) Example 8, 9

In Example 2, except that dichlorotris (triphenylphosphine) ruthenium was replaced with chlorotris (triphenylphosphine) rhodium or dichlorotetrakis (triphenylphosphine) ruthenium, the same amount was used. 36

An absorbent (8) and an absorbent (9) were obtained in the same manner as in Example 2. Table 1 shows the performance evaluation results of these absorbents. Example 10

In a 1-liter glass reaction vessel, 77 g of sodium acrylate, 22.75 g of acrylic acid, 0.25 g of N, N'-methylenebisacrylamide, 329.3 g of deionized water and dichloro (tristriphenyl) (Phosphine) Ruthenium was charged, and while stirring and mixing, 1 g of (B1) was added to keep the temperature of the contents at 3 ° C.

After flowing nitrogen into the contents to reduce the dissolved oxygen content to 1 ppm or less, 1 g of a 1% aqueous solution of hydrogen peroxide, 1.2 g of a 0.2% aqueous solution of ascorbic acid, 1.2 g and 2,2'-azo 2.8 g of a 2% aqueous solution of bisamidinopropane dihydrochloride was added and mixed to initiate polymerization, and the polymerization was carried out for about 5 hours, whereby a water-containing gel-like water-absorbent resin containing (B1) (AB1) I got

(AB1) was chopped to a size of 2 to 5 mm with an internal mixer, and then dried with a ventilation band dryer at 150 ° C and a wind speed of 2. Om / sec. The obtained dried product was pulverized and adjusted to a particle size of 20 to 100 mesh to obtain an absorbent. While 100 g of this absorbent is stirred at high speed, 2 g of a 1% water / methanol mixed solution of ethylene glycol diglycidyl ether (water / methanol = 30/70) is added and mixed, followed by heating and crosslinking at 140 ° C for 30 minutes. As a result, an absorbent (10) was obtained. Table 1 shows the performance evaluation results of the absorbent (10). Example 1 1

A 1-liter glass reactor was charged with 81.75 g of acrylic acid, 0.25 g of N, N'-methylenebisacrylamide and 341 g of deionized water, and the contents were kept at 3 ° C while stirring and mixing. Was. 37

After flowing nitrogen into the contents to reduce the amount of dissolved oxygen to 1 ppm or less, 1 g of a 1% aqueous solution of hydrogen peroxide, 1.2 g of a 0.2% aqueous solution of ascorbic acid and 1.2 g and 2,2'-azo 2.8 g of a 2% aqueous solution of bisamidinopropane dihydrochloride was added and mixed to start polymerization, and polymerization was carried out for about 5 hours to obtain an acid-type hydrogel polymer.

While shredding the hydrogel polymer to a size of 2 to 5 mm with an internal mixer, 109.lg of a 30% aqueous sodium hydroxide solution is added and kneaded to obtain a carboxylic acid group of 72%. A water-containing gel-like water-absorbent resin (A2) in which mol% was neutralized was obtained.

The same amount of (B1) as in Example 1 was added to the hydrogel water-absorbent resin (A2) and mixed uniformly, and then mixed with a ventilated band dryer at 150: wind speed 2. OmZ seconds. Dried.

The obtained dried product was ground to adjust the particle size to 20 to 100 mesh to obtain an absorbent. While stirring 100 g of this absorbent at high speed, add and mix 2 g of a 1% solution of ethylene darikolididicidyl ether in water / methanol (water / methanol = 30/70) and heat-crosslink at 140 ° C for 30 minutes. As a result, an absorbent (11) was obtained. Table 1 shows the performance evaluation results of the absorbent (11). Comparative Example 1.

The hydrogel water-absorbent resin (A1) obtained in Example 1 was shredded to a size of 2 to 5 mm with an internal mixer, and 0.1 g of ethylene glycol diglycidyl ether was added. The mixture was further uniformly mixed with an internal mixer, and then dried with a ventilation band dryer under the conditions of 15 OX and a wind speed of 2. Om / sec.

The obtained dried product was pulverized and adjusted to a particle size of 20 to 100 mesh to obtain a comparative absorbent (a). Table 1 shows the evaluation results of the comparative absorbent (a). 38

Comparative Example 2

The hydrogel-like water-absorbent resin (A1) obtained in Example 1 was cut into a size of 2 to 5 mm with an internal mixer, and then passed through an air-permeable band dryer under the conditions of 1501, wind speed 2. OmZ seconds. Dried. The obtained dried product was pulverized and adjusted to a particle size of 20 to 100 mesh to obtain an absorbent. While stirring 100 g of this absorbent at a high speed, 2 g of a 10% aqueous solution of ethylene dalicol diglycidyl ether (water Z methanol = 30Z70) was added and mixed. By carrying out heat crosslinking for 30 minutes, a comparative absorbent (b) of a surface crosslinked type was obtained. Table 1 shows the performance evaluation results of this comparative absorbent (b). Comparative Example 3

The hydrogel water-absorbent resin (A1) obtained in Example 1 was chopped to a size of 2 to 5 mm with an internal mixer, and then 0.1 g of ethylenedaricol diglycidyl ester and 0.1 g of Nippon Aerosil Add 10 g of 3% aqueous dispersion of AEROS IL 200 (Average particle size 220 nm, primary particle size 12 nm, non-surface area 200 m ² Zg) (Comparative B 1) manufactured by Co., Ltd., and mix evenly with an internal mixer After that, it was dried with a ventilated band dryer at 150 ° C and a wind speed of 2. OmZ seconds. The obtained dried product was pulverized and adjusted to a particle size of 20 to 100 mesh to obtain an absorbent. While stirring 100 g of this absorbent at high speed, 2 g of a 1% water / methanol mixed solution of ethylene glycol diglycidyl ether (water / methanol = 30/70) was added and mixed, followed by heating at 140 ° C for 30 minutes. By cross-linking, a surface cross-linkable absorbent (c) was obtained. Table 1 shows the performance evaluation results of this absorbent (c). Comparative Example 4 39

The hydrogel water-absorbent resin (A1) obtained in Example 1 was shredded to a size of 2 to 5 mm with an internal mixer, and 0.1 g of ethylene dalicol diglycidyl ether was added. After uniform mixing, the mixture was dried using a ventilation band dryer (manufactured by Inoue Metal Industry Co., Ltd.) at 150 ° C and a wind speed of 2.0 m / sec. Next, 0.3 g of (Comparative B1) was added, and the mixture was further uniformly mixed with an internal mixer, and then adjusted to a particle size of 20 to 100 mesh to obtain an absorbent (d). Table 1 shows the performance evaluation results of the absorbent (d).

Table 1 shows the results. table 1

Industrial applicability

The absorbent of the present invention is suitable for absorbing liquid containing water-insoluble and hardly water-soluble components such as menstrual blood and stool. 40

Also, the following effects can be obtained.

(1) Since it has a high diffusion absorption rate and an excellent initial pressure absorption amount (representing the absorption rate under pressure), when used as an absorbent for sanitary goods, for example, it has the effect of improving the initial dry feeling and reducing leakage. Demonstrate.

(2) Water retention Excellent in blood retention and pressure absorption.

(3) Since it is a water-insoluble non-porous spherical single particle having an average particle diameter of 1 to 50 nm, it has excellent powder handling properties. In addition, unlike a granulated product of fine particles, the particles are hardly broken due to mechanical shearing force or friction to generate fine particles.

水 Since it is a water-insoluble, non-porous spherical single particle having an average particle diameter of 1 to 50 nm, it is fibrous even if external force such as vibration is applied when it is mixed with fibrous material such as pulp to form an absorber. Almost no detachment from objects.

改善 Unlike the improvement by the thermal decomposition type foaming agent, there is no generation of radicals etc. during heating and drying, so there is no performance deterioration during the manufacturing process, and not only is the diffusion absorption speed and absorption performance excellent Thus, an absorbent having a low water-soluble component amount can be obtained.

(4) The diffusion and absorption rate can be improved by a simple method of mixing nonporous spherical single particles during the polymerization of the water-absorbent resin or at any stage from after the polymerization to after the drying.

The use of the absorbent article of the present invention is preferably the above-mentioned sanitary article. In addition to hygiene products, urine gelling agents for portable toilets, freshness preservatives for fruits and vegetables, drip absorbents for meat and seafood, cold insulators, disposable warmers, gelling agents for batteries, plants and soil, etc. It is also useful for various uses such as water retention agents, anti-condensation agents, waterproofing agents and packing materials, and artificial snow. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a diagram showing a device for measuring a diffusion absorption rate according to the present invention. 41

The explanation of the symbols is as follows,

1. cook

2. cook

3. Rubber stopper

4. Burette

5. Capillary tube

6. Flat plate with holes

7. Nylon mesh

8. Sample

9. Bovine blood

10. Atmospheric pressure

Claims

42 Claims

1. An absorbent (C) comprising a water-absorbent resin (A) and water-insoluble nonporous spherical single particles (B) having an average particle diameter of 1 to 50 nm.

2. The absorbent (C) according to claim 1, wherein (B) is a water-insoluble non-porous spherical single particle in a water-solubilized state.

3. The absorbent (C) according to claim 1, wherein the specific surface area of (B) is 50 to 400 m ² Zg.

4. The absorbent (C) according to claim 1, wherein (B) is an inorganic water-insoluble nonporous spherical single particle.

5. The absorbent (C) according to claim 4, wherein (B) is an amorphous silicon oxide.

6. The absorbent (C) according to claim 1, wherein (A) is a water-absorbent resin obtained by aqueous solution polymerization of a water-soluble monomer and a first crosslinking agent.

7. The above (A) is a water-absorbent resin obtained by polymerization in the presence of a complex compound (d) of a metal element (dl) and a ligand (d 2) of an anion or a neutral molecule. Item 5. The absorbent (C) according to item 5.

8. The absorbent (C) according to claim 7, wherein the metal element (dl) is a metal element selected from the group IB and the group VIII having 4 to 6 cycles in the long-period periodic table. 43

9. The absorbent according to claim 7, wherein the ligand (d2) of the anion or neutral molecule is one or more selected from the group consisting of the following (1) to (3).

(C).

(1) Anion of atom selected from hydrogen and halogen

(2) Compounds having one or more atoms selected from the group consisting of nitrogen, oxygen, phosphorus, and sulfur

(3) Conjugated compound

10. The metal element (dl) is selected from a group VIII element having five periods, and the ligand (d 2) of the anion or neutral molecule is a halogen ion and a tertiary phosphine compound. The absorbent (C) according to claim 7, which is:

1 1. The absorbent (C) according to claim 1, wherein the amount of (B) is 0.01 to 5% by mass with respect to (A).

12. The absorbent (C) _{0 according to} claim 1, wherein the average particle size of (B) is 10 to 30 nm.

13. The absorbent (C) according to claim 6, wherein (A) is obtained by aqueous polymerization of a water-soluble monomer and a first crosslinking agent, and is further surface-crosslinked with a second crosslinking agent.

14. The (A) is a water-absorbent resin obtained by polymerization in the presence of a complex compound (d) of a metal element (dl) and a ligand (d 2) of an anion or a neutral molecule, 14. The absorbent (C) according to claim 13, wherein (B) is an amorphous gay oxide.

1 5. Water of water-insoluble non-porous spherical single particles (B) having an average particle size of 1 to 50 nm 44

8. The method according to claim 1, wherein the solubilized state is mixed with the dry powder particles of (A), or (A) is added with the water solubilized state of (B) prior to polymerization and drying, followed by heating and drying. The method for producing the absorbent (C) as described above.

1 6. Water-insoluble non-porous spherical single particles (B) having an average particle diameter of 1 to 50 nm in water-solubilized state, and aqueous polymerization of a second crosslinking agent with a water-soluble monomer and a first crosslinking agent Or mixed with the dried powder particles of (A) obtained above and then heat-dried, or mixed with the dried powder particles of (A) and a second crosslinking agent and dried by heating, and the water-solubilized state of (B) 15. The method for producing an absorbent (C) according to claim 13 or 14, wherein a substance is mixed.

1 7. An absorbent structure (F) comprising a matrix of the absorbent (C) according to claim 1, 13 or 14 and a fibrous material (E), wherein the amount of the absorbent (C) is Is 30 to 95% by weight based on the absorbent structure (F).

1 8. An absorbent article (G) comprising the absorbent structure (F) according to claim 17, a liquid-permeable sheet, and a breathable back sheet.

19. Disposable diapers, napkins, no. 19. The absorbent article (G) according to claim 18, wherein the absorbent article (G) is a sanitary product comprising a pad, a paper towel, and a pet sheet.